EP2500778A1 - Toner du type à mémorisation de couleur thermochromique, cartouche comprenant celui-ci renfermée à l'intérieur de celle-ci, appareil de formation d'image, ensemble de cartouche, et ensemble d'appareil de formation d'image - Google Patents

Toner du type à mémorisation de couleur thermochromique, cartouche comprenant celui-ci renfermée à l'intérieur de celle-ci, appareil de formation d'image, ensemble de cartouche, et ensemble d'appareil de formation d'image Download PDF

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Publication number
EP2500778A1
EP2500778A1 EP09851282A EP09851282A EP2500778A1 EP 2500778 A1 EP2500778 A1 EP 2500778A1 EP 09851282 A EP09851282 A EP 09851282A EP 09851282 A EP09851282 A EP 09851282A EP 2500778 A1 EP2500778 A1 EP 2500778A1
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EP
European Patent Office
Prior art keywords
temperature
pigment
decolored
thermochromic
color
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09851282A
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German (de)
English (en)
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EP2500778B1 (fr
EP2500778A4 (fr
Inventor
Katsuyuki Fujita
Yoshiaki Ono
Yutaka Shibahashi
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Pilot Ink Co Ltd
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Pilot Ink Co Ltd
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Publication of EP2500778A4 publication Critical patent/EP2500778A4/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0812—Pretreatment of components
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • C09D11/17—Writing inks characterised by colouring agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/09—Colouring agents for toner particles
    • G03G9/0928—Compounds capable to generate colouring agents by chemical reaction

Definitions

  • the present invention relates to a thermochromic color-memory toner and a cartridge including the same housed therein, an image formation apparatus, a cartridge set, and an image formation apparatus set. More specifically, it relates to a thermochromic color-memory toner which can form a copied matter that can be colored and discolored due to change in temperature and can display only either state in a specific temperature region, a cartridge including the toner housed therein, an image formation apparatus, a cartridge set, and an image formation apparatus set.
  • the present invention intends to remove the defects with the above conventional toner, i.e., it intends to provide a thermochromic color-memory toner that has an excellent function of selectively keeping either of states before and discoloration, a cartridge including the toner housed therein, an image formation apparatus, a cartridge set, and an image formation apparatus set.
  • the present invention has the following constitution.
  • the present invention can provide a convenient thermochromic color-memory toner which can produce a reversible discoloration with showing a wide hysteresis width ( ⁇ H) with respect to color density-temperature curve and has a function of capable of keeping the image formed on a copied matter either in a colored state or in a decolored state, a cartridge including the toner housed therein, an image formation apparatus, a cartridge set, and an image formation apparatus set
  • thermochromic color-memory composition is a composition containing at least three components of (A) an electron donating coloring organic compound, (B) an electron accepting compound capable of causing coloration of the above compound, and (C) a reaction medium controlling color reaction between the above (A) and (B), and which undergoes color change such that a form of a curve obtained by plotting changes in color density with changes in temperature traces along greatly different routes between the case where the temperature is raised from the side lower than a discoloration temperature region and the case where, reversely, the temperature is lowered from the side higher than the discoloration temperature region, and which can selectively keep memory of the colored state in the low-temperature region of a complete coloring temperature (t 1 ) or lower or memory of the decolored state in the high-temperature region of a complete decoloring temperature (t 4 ) or higher in a specific temperature region [a temperature region between t 2 to t 3 (a temperature region where substantially two phases are kept)], and a microcapsule pigment containing the above composition can be
  • FIG. 1 A hysteresis characteristic in the color density-temperature curve of the microcapsule pigment encapsulating the above Thermochromic color-memory composition will be described below.
  • FIG. 1 the color density is plotted on the ordinate and the temperature on the abscissa. A change in the color density due to a temperature change progresses along the arrow.
  • A is a point showing the density at a temperature t 4 at which a completely decolored state is achieved (hereinafter referred to as “complete decoloring temperature”);
  • B is a point showing the density at a temperature t 3 at which decoloring starts (hereinafter referred to as “decoloring starting temperature”);
  • C is a point showing the density at a temperature t 2 at which coloring starts (hereinafter referred to as “coloring starting temperature”);
  • D is a point showing the density at a temperature t 1 at which a completely colored state is achieved (hereinafter referred to as "complete coloring temperature”).
  • the discoloration temperature region is a temperature region between t 1 and t 4 wherein both a colored state and a decolored state can coexist, and a temperature region between t 2 and t 3 wherein difference in color density is large is a substantial discoloration temperature region.
  • the length of the line segment EF is a measure showing contrast of discoloration
  • the length of the line segment HG passing through the midpoint of the line segment EF is a temperature width showing the degree of hysteresis (hereinafter referred to as "hysteresis width ⁇ H").
  • hysteresis width ⁇ H a temperature width showing the degree of hysteresis
  • the discoloration temperatures specifically, by setting the complete coloring temperature t 1 to a temperature that can be obtained only in a freezing compartment, a cold district, or the like, i.e., -50 to 0°C, preferably -40 to -5°C, and more preferably -30 to-10°C, and by setting the complete decoloring temperature t 4 to a temperature that can be obtained by a heater, i.e., 50 to 150°C, preferably 60 to 150°C, and more preferably 70 to 150°C, thereby setting the ⁇ H value being 50 to 100°C, function to maintain color developed in the ordinary conditions (temperature region in daily life) can be effectively exhibited.
  • a heater i.e., 50 to 150°C, preferably 60 to 150°C, and more preferably 70 to 150°C
  • the component (A) of the electron donating coloring organic compound there may be mentioned diphenylmethane phthalides, phenylindolyl phthalides, indolyl phthalides, diphenylmethane azaphthalides, phenylindolyl azaphthalides, fluorans, styrylquinolines, and diazarhodamine lactones.
  • the component (B) of the electron accepting compound there may be mentioned a group of compounds having an active proton, a group of pseudo-acidic compounds (a group of compounds which are not acid but acting as acid in the composition to cause color development of the component (A)), a group of compounds having electron voids and the like.
  • the compounds having an active proton include monophenols and polyphenols as compounds having a phenolic hydroxyl group, those further having a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and an ester or amide thereof, or a halogen group, bis- or tris-phenols, and phenol-aldehyde condensed resins.
  • the compounds may be metal salts of the above compounds having a phenolic hydroxyl group.
  • component (C) a compound represented by the following general formula (1) is preferably used.
  • X represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a methoxy group, or a halogen atom
  • m represents an integer of from 1 to 3
  • n represents an integer of from 1 to 8.
  • Examples of the above compound include diester of glutaric acid and 2-(4-benzyloxyphenyl)ethanol and diester ofpimelic acid and 2-(4-benzyloxyphenyl)ethanol.
  • component (C) a compound represented by the following general formula (2) can also be used.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents an integer of from 0 to 2
  • either of X 1 and X 2 represents -(CH 2 ) n OCOR 2 or -(CH 2 )nCOOR 2 and the other represents a hydrogen atom
  • n represents an integer of from 0 to 2
  • R 2 represents an alkyl group or alkenyl group having 4 or more carbon atoms
  • Y 1 and Y 2 each represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a methoxy group, or a halogen atom
  • r and p each represents an integer of 1 to 3.
  • R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably represents an alkyl group having from 8 to 18 carbon atoms, and more preferably represents an alkyl group having from 8 to 13 carbon atoms.
  • Specific examples of the above compound include 4-benzyloxyphenylethyl octanoate, 4-benzyloxyphenylethyl nonanoate, 4-benzyloxyphenylethyl decanoate, 4-benzyloxyphenylethyl undecanoate, 4-benzyloxyphenylethyl dodecanoate, and 4-benzyloxyphenylethyl tridecanoate.
  • component (C) a compound represented by the following general formula (4) can also be used.
  • R represents an alkyl group or alkenyl group having 11 or more carbon atoms
  • m and n each represents an integer of from 1 to 3
  • X and Y each represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms, or a halogen.
  • Specific examples of the above compounds include 1,1-diphenylmethyl undecanoate, 1,1-diphenylmethyl dodecanoate, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, and 1,1-diphenylmethyl octadecanoate.
  • component (C) a compound represented by the following general formula (5) can also be used.
  • R represents an alkyl group or alkenyl group having from 1 to 21 carbon atoms, and n represents an integer of from 1 to 3.
  • Examples of the above-decribed compounds include diester of 1,3-bis(2-hydroxyethoxy)benzene and caprylic acid, diester of 1,3-bis(2-hydroxyethoxy)benzene and pelargonic acid, diester of 1,3-bis(2-hydroxyethoxy)benzene and capric acid, diester of 1,3-bis(2-hydroxyethoxy)benzene and undecanoic acid, diester of 1,4-bis(hydroxymethoxy) benzene and butyric acid, diester of 1,4-bis(hydroxymethoxy)benzene and valeric acid, diester of 1,4-bis(hydroxymethoxy)benzene and isovaleric acid, diester of 1,4-bis(2-hydroxyethoxy)benzene and acetic acid, diester of 1,4-bis(2-hydroxyethoxy)benzene and propionic acid, and diester of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid.
  • microcapsule pigments As to the shape of the above microcapsule pigment, application of microcapsule pigments with a circular cross-section is not rejected, but those with a noncircular cross-section are effective.
  • the microcapsule pigment has a noncircular cross-section, the pigment is scarcely destroyed by pressure or heat to be applied during the process of preparing toner or in the heat-fixing step. Also, such pigment is easily provided on the surface of a copying paper in a thin and dense state.
  • the microcapsule pigment upon application of pressure of roll in the heat-fixing step, the microcapsule pigment can properly undergo elastic deformation to relax stress, and hence it exhibits the effect of suppressing breakage of capsule wall membrane and, in the heating step, the wall membrane undergoes elastic deformation according to thermal expansion and contraction of the capsule to exhibit the effect of suppressing breakage of capsule wall membrane, whereby the contained thermochromic color-memory composition can be protected to keep the expected thermochromic function.
  • thermochromic color-memory composition in capsules As a method for encapsulating the above thermochromic color-memory composition in capsules, encapsulating methods such as an interfacial polymerization method, an interfacial polycondensation method, an in situ method, and a coacervate method can be applied.
  • the interfacial polymerization method or the interfacial polycondensation method which scarcely causes aggregation or coalescence, is preferably used.
  • the resulting capsule suspension may be diluted, as needed, with water and filtered coarse particles by using a filter to thereby remove the unnecessary coarse particles.
  • filtering materials such as stainless steel net, synthetic resin monofilament net, synthetic resin multifilament net, ultra-fine fiber filter, cotton cloth, unwoven cloth, needle felt, filter paper, etc. may be used alone or in an appropriate combination thereof.
  • thermochromic color-memory toner of the present invention A toner component such as a general-purpose binder resin is applied to the thermochromic color-memory toner of the present invention.
  • the content of the microcapsule pigment in the toner is from 3 to 50% by mass, preferably from 3 to 40% by mass, and more preferably from 5 to 40% by mass. When the content is less than 3% by mass, there results insufficient color density upon coloration, whereas, when the content exceeds 50% by mass, the proportion of the binder resin is so small that fixing properties of the toner is easily deteriorated.
  • the particle diameter of the above thermochromic color-memory toner is from 1 to 15 ⁇ m preferably from 3 to 15 ⁇ m, and more preferably from 3 to 10 ⁇ m.
  • binder resin examples include styrene type resin, vinyl chloride resin, rosin-modified maleic acid resin, chlorinated paraffin, polychlorinated paraffin, phenol resin, epoxy resin, polyester resin, polyamide resin, polyacrylic acid resin, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral, polyurea type resin, terpene resin, polyol resin, hydrogenated petroleum resin, etc.
  • binder resins can be used alone or in combination of two or more thereof.
  • the content of the binder in the toner is effectively from 30 to 97% by mass, preferably from 40 to 97% by mass, and more preferably from 45 to 95% by mass.
  • polyester resins having low temperature fixability are preferably used.
  • the polyester resins those which have a glass transition temperature (Tg) of 30°C to 80°C and preferably 40°C to 70°C, are preferably used.
  • Tg glass transition temperature
  • the glass transition temperature is less than 30°C, blocking resistance (preservability) might be deteriorated in some cases, whereas, when the glass transition temperature exceeds 80°C, the low temperature fixability might be spoiled in some cases.
  • the softening point of the polyester resin is from 105°C to 135°C, preferably from 105°C to 130°C.
  • the softening point is less than 105°C, blocking resistance (preservability) might be deteriorated in some cases, whereas, when the softening point exceeds 130°C, the low temperature fixability might be spoiled in some cases.
  • the content of the polyester resin in the binder resin is preferably from 50% by mass to 98% by mass. When the content is less than 50% by mass, there results poor low temperature fixability, whereas, when the content exceeds 98% by mass, offset resistance might be liable to be spoiled.
  • a release agent such as carbonyl group-containing wax, polyolefin wax, and long-chain hydrocarbon.
  • examples of the above carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkylketones.
  • examples of the above polyolefin wax include polyethylene wax and polypropylene wax.
  • Examples of the above long-chain hydrocarbon include paraffin wax and Sasol wax. Incidentally, the melting point of the above wax is preferably lower than the temperature t 4 of the microcapsule pigment.
  • the above release agents may be used alone or in combination of two or more thereof.
  • a material which is colorless or has an approximately white color is preferred.
  • examples thereof include alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, simple substance of phosphorus or compounds thereof simple substance of tungsten or compounds thereof, fluorine-containing active agents, metal salts of salicylic acid, and metal salts of salicylic acid derivatives,
  • organic fine powder or inorganic fine powder can be used, and examples thereof include fluorine-containing resin powders such as vinylidene fluoride fine powder, and polytetrafluoroethylene fine powder; metal salts of fatty acids such as zinc stearate, calcium stearate, and lead stearate; mental oxides such as iron oxide, aluminum oxide, titanium oxide, and zinc oxide; silica; and silica having been surface-treated with a silane coupling agent, a titanium coupling agent, a silicone oil,
  • thermochromic color-memory toner of the present invention is formed by kneading the microcapsule pigment with the binder resin and other components, and then forming into particles with a predetermined diameter.
  • the softening point of the above toner is from 50 to 120°C, preferably from 60 to 100°C, and more preferably from 60 to 80°C. When the softening point is less than 50°C, blocking is liable to occur within a developing machine.
  • the complete decoloring temperature t 4 of the above microcapsule pigment is preferably a temperature exceeding the softening point of the toner.
  • the softening point (S) of the toner and the temperature t 4 of the above Microcapsule pigment preferably satisfy the following formula (1), and more preferably satisfy the following formula (2).
  • the complete decoloring temperature t 4 of the above microcapsule pigment is a temperature equal to or lower than the softening point of the toner
  • Virgin recording paper can be practically used by realizing the printed image by cooling but, in the case of reusing the recording paper, there arises the problem that not only the printed image but decolored images having been printed in the past appear.
  • the temperature t 4 of the microcapsule pigment to a temperature which satisfies formula
  • (1) expressing relation between the softening point (S) of the toner and the temperature t 4 of the above microcapsule pigment and which is higher than the softening point of the toner by 3°C or higher is an important factor for preventing decoloration of the microcapsule due to variation of heating temperature and for reusing a recording paper
  • the softening point of the toner a load of 20 kg is applied using a plunger to 1g of a toner while heating at a temperature-increasing rate of 5°C/min using a capillary rheometer to extrude through a nozzle of 1 mm in diameter and 1 mm in length, and the temperature at which a half amount of the toner flows out is taken as the softening point.
  • the above toner can be practically used in such a manner of directly placing the toner in an image formation apparatus, or used in such a manner of placing the toner in a cartridge and setting the cartridge on an image formation apparatus.
  • a cartridge for receiving the toner a cartridge can be exemplified which has a electrostatic latent image carrier for carrying an electrostatic latent image and a developing means for developing the electrostatic latent image carried on the electrostatic latent image carrier using a developing agent to thereby form a visible image and which further has, as needed, a charging means, a transfer means, a cleaning means, a neutralizing means, and the like.
  • the above cartridge can be removably mounted on an image formation apparatus such as facsimile and printer.
  • thermochromic color-memory composition containing (A) an electron donating coloring organic compound, (B) an electron accepting compound, and (C) a reaction medium controlling color reaction between the above (A) and (B).
  • the pigment that shows a large hysteresis characteristic with respect to a color density-temperature curve and shows alternativeness between a color-developed state and a colorless state
  • the hysteresis characteristic is that, in a temperature-rise process where the temperature is raised from the color-developed state, decoloration starts when the temperature reaches temperature t 3 and the pigment completely reaches the colorless state in a temperature region of equal to or higher than t 4 which is higher than temperature t 3 , and, in a temperature-drop process where the temperature is lowered from the colorless state, coloration starts when the temperature reaches temperature t 2 which is lower than temperature t 3 and the pigment completely reaches the colored state in a temperature region of equal to or higher than temperature t 1 which is lower than temperature t 2 , with either the colored state or the colorless state being selectively maintained in a temperature region between temperature t 2 and temperature t 3 , and in which the temperature t 1
  • the complete decoloring temperature t 4 By setting the above temperature t 1 to a temperature that can be obtained only in a freezing compartment, a cold district, or the like, i.e., -50 to 0°C, preferably -40 to -5°C and more preferably -30 to -10°C, and by setting the complete decoloring temperature t 4 to a temperature that can be obtained by a frictional member or a heater, i.e., 50 to 150°C, preferably 60 to 150°C and more preferably 70 to 150°C, thereby setting the ⁇ H value being 50 to 100°C, function to maintain color developed in the ordinary conditions (temperature region in daily life) can be effectively exhibited, Incidentally, by setting the complete decoloring temperature t 4 to a temperature attainable by friction heat, i.e., in a range of from 50 to 95°C, preferably from 55 to 90°C and more preferably from 60 to 85°C, handwriting formed on a writing-surface can be sufficiently decolored with friction heat generated
  • the difference in temperature between the complete decoloring temperature t 4 of the microcapsule pigment contained in the toner and the complete decoloring temperature t 4 of the microcapsule pigment contained in the ink of the writing instrument is 10°C or more, preferably 15°C or more, and more preferably 20°C or more.
  • Examples of the ink composition containing a colorant capable of being decolored upon heating include a shear thinning ink containing a shear thinning agent, and a cohesive ink in which microcapsules are suspended in a loosely cohesive state with the aid of an aqueous polymeric cohesive agent. Further, there can be mentioned an ink in which difference in specific gravity between microcapsule pigment and vehicle is adjusted to 0.05 or less.
  • the writing instrument filled with the above ink is a ball-point pen, it is possible to prevent a leakage of the ink from an interval between a ball and a tip when not being used, or to prevent a reverse flowing of the ink when a writing front end is disposed upward (erect state).
  • shear thinning agent examples include xanthan gum, welan gum, succinoglycan (average molecular weight is about 100 to 8,000,000) that is an organic acid modified heteropolysaccharide of which constituent monosaccharides are glucose and galactose, guar gum, locust bean gum and a derivative thereof, hydroxyethylcellulose, an alkyl alginate ester, a polymer containing an alkyl ester of methacrylate as a main component and having a molecular weight of 100,000 to 150,000, glucomannan, a thickening polysaccharide having a gelation ability extracted from seaweeds such as agar or carrageenin, benzyliden sorbitol and benzyliden xylitol or a derivative thereof, a crosslinking acrylic acid polymer, an inorganic fine particulate, polyglycerine fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid este
  • aqueous polymeric cohesive agent there may be mentioned polyvinyl pyrrolidone, polyethylene oxide, aqueous polysaccharide, and aqueous cellulose derivatives
  • aqueous polysaccharide include tragacanth gum, guar gum, pullulan, and cyclodextrin.
  • Specific examples of the aqueous cellulose derivative include methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethylmethyl cellulose, and hydroxypropylmethyl cellulose.
  • any kind of aqueous polymeric cohesive agents that exhibit activity to produce loose bridging between pigment particles can be applied to the above ink, the aqueous cellulose derivative has most effective activity.
  • the aqueous polymeric cohesive agent can be blended in a range of 0.05 to 20% by mass in total ink composition.
  • An aqueous organic solvent can be added as needed into the ink together with water.
  • the organic solvent include ethanol, propanol, butanol, glycerine, sorbitol, triethanolamine, diethanolamine, monoethanolamine, ethyleneglycol, diethyleneglycol, thiodiethyleneglycol, polyethyleneglycol, propyleneglycol, butyleneglycol, ethyleneglycol monomethyl ether, ethyleneglycol monoethyl ether, ethyleneglycol monobutyl ether, diethyleneglycol monomethyl ether, diethyleneglycol monoethyl ether, diethyleneglycol monobutyl ether, propyleneglycol monobutyl ether, ethyleneglycol monomethyl ether acetate, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone.
  • the abrasion of a ball receiving sheet is prevented by adding lubricants including higher fatty acids such as oleic acid, non-ionic surfactants having a long chain alkyl group, polyether modified silicone oil, thiophosphorous acid triesters such as thiophosphorous acid tri(alkoxycaxbonyl methyl ester) or thiophosphorous acid tri(alkoxycarbonyl ethyl ester), phosphoric acid monoester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, phosphoric acid diester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, and metal salts, ammonium salts, amine salts, and alkanolamine salts thereof.
  • lubricants including higher fatty acids such as oleic acid, non-ionic surfactants having a long chain alkyl group, polyether modified silicone oil, thiophosphorous acid triesters such as thiophosphorous acid tri(alkoxyca
  • resins such as acryl resins, a styrene-maleic acid copolymer, a cellulose derivative, polyvinyl pyrrolidone, polyvinyl alcohol, and dextrin may be added to impart a fixing property to the surface of the paper or viscosity
  • inorganic salts such as sodium carbonate, sodium phosphate, and sodium acetate
  • pH controlling agents such as an organic basic compound such as an aqueous amine compound
  • an anticorrosive agents such as benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, and saponin
  • antiseptics or antifungal agents such as phenic acid, a sodium salt of 1,2-benzthiazoline 3-one, sodium benzoate, sodium dihydroacetate, potassium sorbate, paraoxypropylbenzoate, and 2,3,5,6-tetrachloro-4
  • a writing instrument can be obtained by filling the above ink into an instrument such as ball-point pen or marking pen that has a marking pen tip or ball-point pen tip mounted on a writing front end.
  • the structure and shape of the ball-point pen are not particularly limited. Examples thereof includes a ball-point pen having an ink receiving tube in which a shear thinning ink is filled in an axle body, in which the ink receiving tube is connected with a tip where a ball is mounted on its front end, and a liquid plug for preventing reverse flowing is closely contacted in the edge of the ink.
  • the ball-point pen tip will be explained in more detail.
  • a tip formed by holding a ball in a ball holding part in which the vicinity of a front end of a metal pipe is pressed and deformed inwardly from the outside a tip formed by holding a ball in a ball holding part formed by cutting a metal material by a drill and the like; a tip in which a ball receiving sheet made of a resin is provided in the tip made of metal or plastic; or a tip in which a ball held in the tip is pressed in a front direction by a spring body.
  • the ball made of cemented carbide, stainless steel, ruby, ceramic, resin, rubber, and the like, and having a diameter of about 0.3 to 3.0 mm, preferably 0,3 to 1.5 mm, and more preferably 0.4 to 1.0 mm can be applicable.
  • the ink receiving tube receiving ink for example, a molded body formed of a thermoplastic resin such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used.
  • the ink receiving tube and the tip may be connected through a connection member (holder).
  • the ink receiving tube may be a refill type in which the refill is received into an axle body made of a resin or metal, or the ink may be directly filled in an axle body in which the axle body mounting a tip in the front end thereof is used itself as an ink receiving body.
  • An ink follower is filled in a rear end of ink received in the ink receiving tube.
  • the composition of the ink follower includes a non-volatile liquid or a hardly volatile liquid.
  • a non-volatile liquid or a hardly volatile liquid include vaseline, spindle oil, castor oil, olive oil, mineral oil refineries, liquid paraffine, polybutene, ⁇ -olefine, oligomer or cooligomer of ⁇ -olefine, dimethyl silicone oil, methylphenyl silicone oil, amino modified silicone oil, polyether modified silicone oil, and fatty acid modified silicone oil. It can be used alone or in combination of two or more thereof.
  • the viscosity of the non-volatile liquid and/or the hardly volatile liquid is increased to a suitable viscosity by adding a thickening agent.
  • the thickening agent include silica having hydrophobic treated surface; particulate silica having a methylated surface; aluminum silicate; swellable mica; a clay-based thickening agent such as hydrophobic treated bentonite or montmorillonite; fatty acid metal soaps such as magnesium stearate, calcium stearate, aluminum stearate, and zinc stearate; tribenzylidene sorbitol; fatty acid amide; amide modified polyethylene wax; hydrogenated castor oil; a dextrin-based compound such as fatty acid dextrin; and a cellulose-based compound.
  • the liquid ink follower may be used in combination with a solid ink follower.
  • the structure and shape of the marking pen are not particularly limited. Examples thereof include a marking pen in which an ink occlusion body formed of a fiber bundle is embedded in an axle body, a marking pen tip formed of a processed fiber having a capillary gap therein is mounted directly or via a connection member (holder) on the axle body, and a cohesive ink is impregnated in the ink occlusion body of the marking pen formed by connecting the ink occlusion body and the tip, or a marking pen in which a tip and an ink receiving tube are arranged through a valve body that opens by pressing the pen-front and the ink is directly received in the ink receiving tube.
  • the tip is a generally known porous member having communication pores of which porosity is selected within the range of about 3 0 to 70%, made of processed resin of fibers, fusion processed bodies of hot-melt fiber, or a felt, and the tip is provided for practical use by processed its one end into a form depending on the purpose, such as a cannonball form, a rectangular form, or a chisel.
  • the ink occlusion body is configured by bundling crimped fibers in a length direction, incorporating the fibers into a covering material such as a plastic tube or a film, and adjusting its porosity within a range of about 40 to 90%.
  • the valve body use can be made of a generally known pumping type, and also preferable one is those which a spring pressure of is adjusted so as to enable the valve open by pen pressure.
  • the shape of the writing instrument is not limited to the shapes mentioned above, and may be a multiple writing instrument (i.e., a both head type or a pen-front drawing type) in which tips of different type are provided or tips for introducing inks of different colors are provided.
  • the handwriting obtained by writing on a writing-surface using the above writing instrument can be discolored by heating.
  • heating means a drier or a finger rubbing method can be used, but it is preferable that discoloration is instrumented by friction using a frictional member.
  • a frictional member an elastic member such as an elastomer or a plastic foamed body, which has a good elasticity and can generate friction heat by an appropriate friction is preferable.
  • a plastic molded body, stone, wood, metal, and cloth may be used as well.
  • Examples of a material of the frictional member include a silicone resin, SBS resin (styrene-butadiene-styrene copolymer), and SEBS resin (styrene-ethylene-butylene-styrene block copolymer).
  • thermochromic color-memory composition composed of 4.5 parts of 2-(2-chloroamino)-6-dibutylaminofluoran as component (A), 5.0 parts of 2,2-bis(4'-hydroxyphenyl) hexafluoropropane as component (B) and 50 parts of diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol as component (C) and blending 25.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall membrane material and 50,0 parts of a co-solvent was emulsified and dispersed in a 8% polyvinyl alcohol aqueous solution into fine droplets, followed by continuous stirring under heating, and 2.5 parts of a water-soluble aliphatic modified amine was added thereto, followed by further continuous stirring to obtain a microcapsule pigment suspension.
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 77°C, and a complete coloring temperature of -12°C, and undergoes discoloration from black to colorless due to change in temperature.
  • the resulting mixture was melt-kneaded in a twin-screw extruder at a kneading temperature of 90°C. Then, the product was solidified by cooling, followed by pulverizing and classifying to obtain a thermochromic color-memory toner having a particle diameter of 7 ⁇ m. The toner particles had a softening point of 73°C.
  • thermochromic color-memory toner previously cooled to develop the color of the microcapsule pigment
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a thermochromic image, whereby a thermochromic copied matter was obtained.
  • the copied matter was visually confirmed to carry thereon a black thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 77°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 1.5 parts of 2-(dibutylamino)-8-(dipentylamino)-4-methyl-spiro[5H-[1]benzopyrano[2,3-g]-pyrimidine-5,1'(3'H)-isobenzofuran]-3-one as component (A), 5.0 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol as component (C) and blending 25.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall membrane material and 50.0 parts of a co-solvent was emulsified and dispersed in a 8% polyvinyl alcohol aqueous solution into fine droplets, followed by continuous stirring under heating, and 2.5 parts of a water-soluble aliphatic modified amine was added thereto,
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 78°C, and a complete coloring temperature of -11 °C, and undergoes discoloration from pink to colorless due to change in temperature.
  • the resulting mixture was melt-kneaded in a twin-screw extruder at a kneading temperature of 90°C. Then, the product was solidified by cooling, followed by pulverizing and classifying to obtain a Thermochromic color-memory toner having a particle diameter of 7 ⁇ m. The toner particles had a softening point of 73°C.
  • thermochromic color-memory toner previously cooled to develop the color of the microcapsule pigment
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a thermochromic image, whereby a thermochromic copied matter was obtained.
  • the copied matter was visually confirmed to carry thereon a pink thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 78°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 3.0 parts of 4-[2,6-bis(2-ethoxyphenyl)-4-pyridinyl]-N,N-dimethylbenzeneamine as component (A), 10.0 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol as component (C) and blending 25.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall membrane material and 50.0 parts of a co-solvent was emulsified and dispersed in a 8% polyvinyl alcohol aqueous solution into fine droplets, followed by continuous stirring under heating, and 2.5 parts of a water-soluble aliphatic modified amine was added thereto, followed by further continuous stirring to obtain a microcapsule pigment suspension.
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 76°C, and a complete coloring temperature of -10°C, and undergoes discoloration from yellow to colorless due to change in temperature.
  • thermochromic color-memory toner having a particle diameter of 7 ⁇ m.
  • the toner particles had a softening point of 73°C.
  • thermochromic color-memory toner previously cooled to develop the color of the microcapsule pigment
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a thermochromic image, whereby a thermochromic copied matter was obtained.
  • the copied matter was visually confirmed to carry thereon a yellow thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 76°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 1 part of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5.0 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanol as component (C) and blending 25.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall membrane material and 50.0 parts of a co-solvent was emulsified and dispersed in a 8% polyvinyl alcohol aqueous solution into fine droplets, followed by continuous stirring under heating, and 2.5 parts of a watersoluble aliphatic modified amine was added thereto, followed by further continuous stirring to obtain a microcapsule pigment suspension.
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 79°C, and a complete coloring temperature of -10°C, and undergoes discoloration from blue to colorless due to change in temperature.
  • the resulting mixture was melt-kneaded in a twin-screw extruder at a kneading temperature of 90°C. Then, the product was solidified by cooling, followed by pulverizing and classifying to obtain a thermochromic color-memory toner having a particle diameter of 7 ⁇ m. The toner particles had a softening point of 73°C.
  • thermochromic color-memory toner previously cooled to develop the color of the Microcapsule pigment
  • the cartridge was set on a laser printer, and a document for meeting was copied to form a thermochromic image, whereby a thermochromic copied matter was obtained.
  • the copied matter was visually confirmed to carry thereon a blue thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 79°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory toners obtained in Examples 1 to 4 were placed in a cartridge.
  • the cartridge was set in a laser printer, and a photograph of landscape was copied to form a thermochromic image and obtain a thermochromic copied matter.
  • the copied matter was visually confirmed to carry thereon a multi-calor thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 79°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a Thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 1.0 part of 1,2-benz-6-(N-ethyl-N-isoamylamino) fluoran and 2.0 parts of 1,3-dimethyl-6-diethylaminofluoran as components (A), 4.5 parts of 4,4'-(2-memylpropylideno)bisphenol and 7.5 parts of 2,2-bis(4'-hydroxyphenyl) hexafluoropropane as components (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C) was obtained. The resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2,5 ⁇ m, a complete decoloring temperature of 57°C, and a complete coloring temperature of -20°C, and undergoes discoloration from red to colorless due to change in temperature.
  • a reversible thermochromic aqueous ink composition was prepared by blending 25.7 parts of the above microcapsule pigment, 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.2 part of a modified silicone type antifoaming agent, 0.1 part of an antifungal agent, 1.0 part of a lubricant, 1.0 part of triethanolamine, and 58.8 parts of water.
  • a polypropylene-made pipe (an ink receiving tube 21) was filled by suction with the above ink 4 (previously cooled to -20°C or lower to develop red color of the microcapsule pigment, then allowed to stand at room temperature) and was connected, via a resin-made holder 22, with a ball-point pen tip 3.
  • an ink follower 5 liquid plug
  • polybutene as a main component and having viscoelasticity
  • the refill 2 was placed in an axle body 6 (composed of a front axle body and a rear axle body), a cap 7 was fitted thereto, and then degassing treatment was carried out by centrifugation, whereby a writing instrument 1 (ball-point pen) was obtained.
  • the above ball-point pen tip is made of a metal material and holds a cemented carbide ball of 0.5 mm in diameter in its ball-holding part formed by cutting the metal material with a drill, with the ball being pressed in the front direction by means of a spring body.
  • an SEBS resin-made frictional member 8 is fitted to the rear axle body end.
  • thermochromic copied matter was obtained.
  • a black thermochromic image was visually observed at room temperature (25°C), and red letters (handwriting) could be written on the copied matter using the above ball-point pen.
  • red letters could be written on the copied matter using the above ball-point pen.
  • part of the handwriting was rubbed by using the frictional member, it was decolored to become colorless.
  • both the thermochromic image and the handwriting were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermo chromic image, whereby the recording paper was able to be used repeatedly,
  • thermochromic color-memory composition composed of 2,0 parts of 4,5,6,7-tetrachloro-3-[4-(dimethylamino)-2-methylphenyl]-3-(1-ethyl-2-methyl-1H-indol-3-yl)-1(3H)-isobenzofuranon as component (A), 3.0 parts of 4,4'-(2-ethylhexane-1,1-diyl)diphenol and 5.0 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane as components (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C) was obtained.
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 55°C, and a complete coloring temperature of -20°C, and undergoes discoloration from blue to colorless due to change in temperature.
  • thermochromic aqueous ink composition was prepared by blending 20.0 parts of the above microcapsule pigment (previously cooled to -20°C or lower to develop blue color), 0.5 part of hydroxyethyl cellulose, 0.2 part of a polymer dispersant, 1.0 part of an antiseptic, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of an antifoaming agent, and 52.78 parts of water.
  • An ink occluding body 10 formed of a polyester sliver covered with a synthetic resin film was impregnated with the above ink composition, and was placed in a axle body 6 formed of a polypropylene resin, and connected, via a holder 22, with a marking pen tip 3 (cannonball form) made of resin-processed polyester fibers at a front end of the axle body, and a cap 7 was fitted to obtain a writing instrument 1 (marking pen).
  • An SEBS resin as a frictional member 8 was fitted to the axle body rear end.
  • thermochromic copied matter was obtained.
  • a pink thermochromic image was visually observed at room temperature (25°C), and blue letters (handwriting) could be written on the copied matter using the above marking pen.
  • part of the handwriting was rubbed by using the frictional member, it was decolored to become colorless.
  • the copied matter was heated to 78°C or higher, both the thermochromic image and the handwriting were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (255°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 4.5 parts of 2-(2-chloroamino)-6-dibutylaminofluoran as component (A), 4.5 parts of 4,4'-(2-methylpropylidene)bisphenol and 7.5 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane as components (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C) was obtained.
  • the resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 57°C, and a complete coloring temperature of -20°C, and undergoes discoloration from black to colorless due to change in temperature.
  • a reversible thermochromic aqueous ink composition was prepared by blending 25.7 parts of the above Microcapsule pigment, 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.2 part of a modified silicone type antifoaming agent, 0.1 part of an antifungal agent, 1.0 part of a lubricant, 1.0 part of triethanolamine, and 58.8 parts of water.
  • a polypropylene-made axle body 6 of 7.0 mm in inside diameter and 10 mm in outside diameter fixedly fitted with a ball-point pen tip 3 at a front end thereof was filled with the above ink 4 (previously cooled to -20°C or lower to develop black color of the microcapsule pigment, then allowed to stand at room temperature), and then an ink follower 5containing polybutene as a main component and having viscoelasticity was filled therein, and an SEBS resin-made frictional member 8 was fitted to the axle body rear end. Further, a cap 7 was fitted thereto, and degassing treatment was carried out by centrifugation, whereby a writing instrument (ball-point pen) 1 was obtained.
  • the above ball-point pen tip is made of a metal material and holds a cemented carbide ball of 0.7 mm in diameter in its ball-holding part formed by cutting the metal material with a drill, with the ball being pressed in the front direction by means of a spring body.
  • thermochromic copied matter was obtained.
  • a black thermochromic image was visually observed at room temperature (25°C), and black letters (handwriting) could be written on the copied matter using the above ball-point pen.
  • part of the handwriting was rubbed by using the fictional member, it was decolored to become colorless.
  • the copied matter was heated to 77°C or higher, both the thermochromic image and the handwriting were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 3.0 parts of 4-[2,6-bis(2-ethoxyphenyl)-4-puridinyl]-N,N-dimethylbenzeneamine as component (A), 10.0 parts of 2,2-bis(4'-hydroxyphenyl)-hexafluoropropane as component (B), and 50.0 parts of 4-benzyloxyphenylethyl caprate as component (C) was obtained. The resulting suspension was subjected to centrifugation to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 59°C, and a complete coloring temperature of -20°C, and undergoes discoloration from yellow to colorless due to change in temperature.
  • a reversible thermochromic aqueous ink composition was prepared by blending 25.0 parts of the above microcapsule pigment (previously cooled to -20°C or lower to develop yellow color), 0.5 part of hydroxyethyl cellulose, 0.2 part of a polymer dispersant, 1.0 part of an antiseptic, 0.5 part of polyvinyl alcohol, 25.0 parts of glycerin, 0.02 part of an antifoaming agent, and 47.78 parts of water.
  • a stirring body 9 (SUS-304 ferrite type stainless steel ball; diameter: 3 mm) were placed in an axle body 6, and the axle body 6 was fitted, via a holder 22, with a marking pen tip 3 [chisel-type fibrous pen body (porosity: about 53%)] on a front end thereof, and a cap 7 was fitted to obtain a direct liquid type writing instrument 1 (marking pen).
  • a valve mechanism 11 is provided in the axle body, and the valve mechanism is a mechanism which is composed of a valve seat, a valve body, and a metal-made spring functioning to press the valve body against the valve seat, and which functions so that, upon writing, the valve opens due to writing pressure applied to a pen body.
  • An SEBS resin as a frictional member 8 was fitted to the axle body rear end.
  • thermochromic copied matter was obtained.
  • a blue thermochromic image was visually observed at room temperature (25°C), and yellow highlight could be formed on the image using the above marking pen.
  • the frictional member When part of the handwriting was rubbed by using the frictional member, it was decolored to become colorless.
  • the copied matter was heated to 79°C or higher, both the Thermochromic image and the highlight were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper-was able to be used repeatedly.
  • a suspension of a microcapsule pigment encapsulating a Thermochromic color-memory composition composed of 1.5 parts of 2-(dibutylamino)-8-(dipentylamino)-4-methyl-spiro[5H-[1]benzopirano[2,3-g]pyrimidine-5,1'-(3'H)-isobenzofuran]-3-one as component (A), 5.0 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane as component (B), and 50.0 parts of diester of pimelic acid and 2-(4-benzyloxyphenyl)ethanolyl as component (C) was obtained. The resulting suspension was subjected to centrifugation to isolate the Microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 78°C, and a complete coloring temperature of -11°C, and undergoes discoloration from pink to colorless due to change in temperature.
  • a reversible thermochromic aqueous ink composition was prepared by blending 25.7 parts of the above microcapsule pigment, 0.2 part of succinoglycan (shear thinning agent), 5.5 parts of urea, 7.5 parts of glycerin, 0.2 part of modified silicone type antifoaming agent, 0.1 part of an antifungal agent, 1.0 part of a lubricant, 1.0 part of triethanolamine, and 58.8 parts of water.
  • a polypropylene-made pipe (an ink receiving tube 21) was filled by suction with the above ink 4 (previously cooled to -11°C or lower to develop pink color of the microcapsule pigment, then allowed to stand at room temperature) and was connected, via a resin-made holder 22, with a ball-point pen tip 3.
  • an ink follower 5 liquid plug
  • polybutene as a main component and having viscoelasticity
  • the refill 2 was placed in an axle body 6 (composed of a front axle body and a rear axle body), a cap 7 was fitted thereto, and then degassing treatment was carried out by centrifugation, whereby a writing instrument 1 (ball-point pen) was obtained.
  • the above ball-point pen tip is made of a metal material and holds a cemented carbide ball of 0.5 mm in diameter in its ball-holding part formed by cutting the metal material with a drill, with the ball being pressed in the front direction by means of a spring body.
  • thermochromic copied matter was obtained.
  • a black thermochromic image was visually observed at room temperature (25°C), and pink letters (handwriting) could be written on the copied matter using the above ball-point pen.
  • thermochromic image and the handwriting were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory toners obtained in Examples 1 to 4 (previously cooled to develop a color of each microcapsule pigment) was placed in a cartridge.
  • the writing instrument obtained in Example 8 was combined with the above cartridge to obtain a cartridge set.
  • the cartridge was set on a laser printer, and a document for meeting was copied to form a colorful thermochromic image, whereby a thermochromic copied matter was obtained.
  • a black handwriting could be formed on the copied matter by using the above writing instrument. When part of the handwriting was rubbed by using the frictional member, it was decolored to become colorless.
  • thermochromic image and the handwriting were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • the cartridge obtained in Example 1 was combined with the writing instruments obtained in Examples 6 to 9 to obtain a cartridge set.
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a black thermochromic image, whereby a thermochromic copied matter was obtained.
  • Red, blue, black, and yellow handwritings could be formed on the above copied matter by using the above writing instruments.
  • part of the handwritings was rubbed by using the frictional member, they were decolored to become colorless.
  • the copied matter was heated to 77°C or higher, both the thermochromic image and the handwritings were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory toners of Examples 1 to 4 (previously cooled to develop a color of each microcapsule pigment) was placed in a cartridge.
  • the writing instruments obtained in Examples 6 to 9 were combined with the above cartridge to obtain a cartridge set.
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a color thermochromic image, whereby a thermochromic copied matter was obtained. Red, blue, black, and yellow handwritings could be formed on the copied matter by using the above writing instruments. When a part of the handwritings was rubbed by using the frictional member, they were decolored to become colorless.
  • thermochromic image and the handwritings were decolored and returned to a state before use (recording paper on which nothing is copied) at a room temperature (25°C).
  • a copied matter can be obtained by setting the recording paper in the laser printer and conducting copying procedures to thereby form a thermochromic image, whereby the recording paper was able to be used repeatedly.
  • thermochromic color-memory composition composed of 1 part of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 3.0 parts of 2,2-bis(4'-hydroxyphenyl)hexafluoropropane and 3.0 parts of 1,1-bis(4-hydroxyphenyl)-n-decane as components (B), and 50 parts of diester of 1,4-bis(2-hydroxyethoxy)benzene and caproic acid as component (C) and blending 25.0 parts of an aromatic polyvalent isocyanate prepolymer as a wall membrane material and 50.0 parts of a co-solvent was emulsified and dispersed in a 8% polyvinyl alcohol aqueous solution into fine droplets, followed by continuous stirring under heating, and 2.5 parts of a water-soluble aliphatic modified amine was added thereto, followed
  • the resulting suspension was subjected to centrifugation, to isolate the microcapsule pigment.
  • the above microcapsule pigment has an average particle diameter of 2.5 ⁇ m, a complete decoloring temperature of 80°C, and a complete coloring temperature of -7°C, and undergoes discoloration from blue to colorless state due to change in temperature.
  • the resulting mixture was melt-kneaded in a twin-screw extruder at a kneading temperature of 90°C. Then, the product was solidified by cooling, followed by pulverizing and classifying to obtain a thermochromic color-memory toner having a particle diameter of 7 ⁇ m. The toner particles had a softening point of 77°C.
  • thermochromic color-memory toner previously cooled to develop the color of the microcapsule pigment
  • the cartridge was set in a laser printer, and a document for meeting was copied to form a thermochromic image, whereby a thermochromic copied matter was obtained.
  • the copied matter was visually confirmed to carry thereon a blue Thermochromic image at room temperature (25°C).
  • the thermochromic image was decolored upon heating to a temperature of 80°C or higher and, at a room temperature (25°C), the copied matter returned to the state before use (recording paper on which nothing is copied).
  • a copied matter can be obtained by setting the recording paper on the laser printer and conducting copying procedures to thereby form a Thermochromic image, whereby the recording paper was able to be used repeatedly.
  • the present invention can provide a convenient thermochromic color-memory toner which can produce a reversible discoloration with showing a wide hysteresis width ( ⁇ H) with respect to color density-temperature curve and has a function of capable of keeping the image formed on a copied matter either in a colored state or in a decolored state, a cartridge including the toner housed therein, an image formation apparatus, a cartridge set, and an image formation apparatus set.
  • ⁇ H hysteresis width

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  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
EP09851282.5A 2009-11-13 2009-11-13 Toner du type à mémorisation de couleur thermochromique, cartouche comprenant celui-ci renfermée à l'intérieur de celle-ci, appareil de formation d'image, ensemble de cartouche, et ensemble d'appareil de formation d'image Active EP2500778B1 (fr)

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Application Number Priority Date Filing Date Title
PCT/JP2009/069384 WO2011058652A1 (fr) 2009-11-13 2009-11-13 Toner du type à mémorisation de couleur thermochromique, cartouche comprenant celui-ci renfermée à l'intérieur de celle-ci, appareil de formation d'image, ensemble de cartouche, et ensemble d'appareil de formation d'image

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EP2500778A1 true EP2500778A1 (fr) 2012-09-19
EP2500778A4 EP2500778A4 (fr) 2016-01-13
EP2500778B1 EP2500778B1 (fr) 2017-10-25

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Country Status (6)

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US (1) US9005857B2 (fr)
EP (1) EP2500778B1 (fr)
JP (1) JP5396651B2 (fr)
KR (1) KR101731134B1 (fr)
CN (1) CN102713762A (fr)
WO (1) WO2011058652A1 (fr)

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WO2017036604A1 (fr) * 2015-09-03 2017-03-09 Thermographic Measurements Ltd Indicateur sensible à la température
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Also Published As

Publication number Publication date
WO2011058652A1 (fr) 2011-05-19
EP2500778B1 (fr) 2017-10-25
EP2500778A4 (fr) 2016-01-13
CN102713762A (zh) 2012-10-03
JP5396651B2 (ja) 2014-01-22
US9005857B2 (en) 2015-04-14
JPWO2011058652A1 (ja) 2013-03-28
KR20120115223A (ko) 2012-10-17
KR101731134B1 (ko) 2017-04-27
US20130029257A1 (en) 2013-01-31

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